Synthesis of Saxitoxin Biosynthetic Intermediates: Reveal the Mechanism for Formation of its Tricyclic Skeleton in Biosynthesis
Abstract: The synthesis and biosynthesis of the complex saxitoxin (STX) structure have garnered significant interest. Previously, we hypothesized that the tricyclic skeleton of STX originates from the monocyclic precursor 11‐hydroxy‐IntC’2 during biosynthesis, although direct evidence has been lacking. In this study, we identified conditions to synthesize a proposed tricyclic biosynthetic intermediate, 12,12‐dideoxy‐decarbamoyloxySTX (dd‐doSTX), along with its 6‐epimer (6‐epi‐dd‐doSTX) and a bicyclic compound, in a single step from di‐Boc protected 11‐hydroxy‐IntC’2. The reaction mechanism involves successive aza‐Michael addition of a guanidino amine to the conjugated olefin. Notably, both dd‐doSTX and 6‐epi‐dd‐doSTX were detected in a toxin‐producing cyanobacterium, suggesting that the biosynthetic enzymes may generate these compounds via similar mechanisms.
- Standort
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Deutsche Nationalbibliothek Frankfurt am Main
- Umfang
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Online-Ressource
- Sprache
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Englisch
- Erschienen in
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Synthesis of Saxitoxin Biosynthetic Intermediates: Reveal the Mechanism for Formation of its Tricyclic Skeleton in Biosynthesis ; day:31 ; month:10 ; year:2024 ; extent:8
Chemistry ; (31.10.2024) (gesamt 8)
- Urheber
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Hirozumi, Ryosuke
Hakamada, Mayu
Minowa, Takashi
Cho, Yuko
Kudo, Yuta
Konoki, Keiichi
Oshima, Yasukatsu
Nagasawa, Kazuo
Yotsu‐Yamashita, Mari
- DOI
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10.1002/asia.202400834
- URN
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urn:nbn:de:101:1-2411011330131.949646352357
- Rechteinformation
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Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
- Letzte Aktualisierung
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15.08.2025, 07:24 MESZ
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Beteiligte
- Hirozumi, Ryosuke
- Hakamada, Mayu
- Minowa, Takashi
- Cho, Yuko
- Kudo, Yuta
- Konoki, Keiichi
- Oshima, Yasukatsu
- Nagasawa, Kazuo
- Yotsu‐Yamashita, Mari
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